JP2017528536A - Polyurethane aerosol compositions, articles, and related methods - Google Patents

Abstract

One-part, storage-stable polyurethane aerosol compositions, and related articles and methods are provided. When sprayed onto a substrate and dried, these compositions provide a polyurethane film. These polyurethane films exhibit improved moisture resistance, optical clarity, and weather resistance, especially under harmful environmental conditions, compared to known aerosol compositions. The composition is generally a urethane moiety obtained by reacting (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water solubilizing compound, and (iii) a diisocyanate. And optionally containing silane end groups, an aqueous polyurethane dispersion, a propellant, and optionally one or more additives.

Description

(Cross-reference of related applications)
This application claims priority from US Provisional Patent Application No. 61/016221 (filed June 24, 2014), the entire disclosure of which is incorporated herein by reference.

(Field of Invention)
Sprayable polyurethane compositions and related articles and methods are provided. The sprayable polyurethane composition is more specifically a polyurethane aerosol composition.

  Polyurethane is a synthetic polymer found in a wide range of commercial and industrial applications. These polymers characterized by carbamate (—NH—CO—O—) chemical bonds can be obtained by methods known in the art, for example by reacting a polyfunctional isocyanate with a diol or polyol in the presence of a suitable catalyst. Manufactured. Thermoplastic polyurethanes are characterized by linear polymer chains that form a self-ordered block structure, whereas thermosetting polyurethanes form covalently crosslinked networks. Through judicious selection of diisocyanates and diol or polyol components, polyurethanes can be designed to be resistant to moisture and chemical degradation while also exhibiting high flexibility and toughness.

  The aforementioned properties make polyurethane coatings and films particularly useful in harsh outdoor environments. In many applications, the polyurethane coating can serve a decorative purpose while also protecting the underlying substrate from environmental weathering, chemical exposure, heat, and / or abrasion. The use of polyurethane in protective film applications is described, for example, in US Pat. Nos. 6,607,831 (Ho et al.) And 6,383,644 (Fuchs).

  Recently, polyurethane films can be coated onto substrates by aerosol spraying. Aerosol spraying involves enclosing a liquid composition and a volatile propellant in a common container and then extruding the composition from the container using positive pressure generated by the propellant. For example, 3M brand Paint Defender Spray Film uses a polyurethane composition that can be sprayed onto the exterior of an automobile and then dried to form a transparent and durable protective coating. Aerosol products are attractive to end users because they are easy to use, have high storage stability, do not require mixing, and can provide a very smooth and uniform film.

  Despite its many advantages, polyurethane aerosol compositions may be limited by certain technical problems. In particular, in the case of aqueous polyurethane aerosol compositions, the main problem is insufficient moisture resistance. Until the polyurethane is completely or nearly completely dry, the composition can be vulnerable to moisture absorption. If exposed to rain, washing, or even a humid environment immediately after the initial application, the resulting film may lose its transparency and become cloudy or even opaque. Conventional polyurethanes also have the problem of tending to yellow when exposed to sunlight.

  Provided herein are polyurethane aerosol compositions based on aqueous polyurethane dispersions. These dispersions can provide a thermosetting or thermoplastic polyurethane film when sprayed onto a substrate and dried. These films have been found to exhibit superior moisture resistance, heat resistance, and UV resistance, optical clarity, and mechanical properties compared to known aerosol compositions, particularly under harmful environmental conditions. For example, in a final cured film, a gravelometer rating of at least 5 (measured according to ASTM D-3170) is preferred and achieved. These qualities make the provided composition very suitable for outdoor applications such as automotive paint protection films where both aesthetics and protection from rock fragments, dirt and debris are important. . Advantageously, these polyurethane films have also been found to exhibit strong adhesion on glass substrates while retaining the ability to be manually removed from the substrate at the end of the period of use.

  In a first aspect, a polyurethane aerosol composition comprising a polymer, water and a propellant, wherein the polymer comprises (i) a polyol or thiol having an isocyanate-reactive functional group, and (ii) neutralized water. A polymer obtained by reacting a solubilizing compound, (iii) a diisocyanate, and (iv) an isocyanate-reactive chain extender comprising hydrazine or hydrazide, when the composition is deposited on a substrate A composition is provided that forms a transparent or transparent film.

  In a second aspect, a polyurethane aerosol composition comprising a urethane moiety, a silyl end group, water and a propellant, wherein the urethane moiety is (i) a polyol or thiol having an isocyanate-reactive functional group, Provided is a composition that is a urethane moiety obtained by reacting (ii) a neutralized water solubilizing compound and (iii) diisocyanate.

  In a third aspect, a method for producing a polyurethane aerosol composition is provided. The method includes the steps of obtaining an isocyanate-terminated polyurethane prepolymer by reacting a polyol component comprising a polyol or thiol containing two isocyanate-reactive groups and a mixture comprising a diisocyanate; a step of providing a solubilized polyurethane prepolymer by sequentially reacting i) an acidic water-solubilizing compound and (ii) a base for neutralizing the water-solubilizing compound; Dispersing the polymer in water; reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender comprising hydrazine or hydrazide; adding a propellant to obtain a polyurethane aerosol composition; including.

  In a fourth aspect, a method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition, wherein the method uses a propellant and through an aerosol actuator, the substrate. Depositing an aqueous polyurethane dispersion on the material, wherein the aqueous polyurethane dispersion comprises (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water solubilizing compound, and (iii) A polymer obtained by reacting a) diisocyanate with (iv) an isocyanate-reactive chain extender containing hydrazine or hydrazide, and removing water from the dispersion to cure the thermoplastic polyurethane coating And providing a method.

  In a fifth aspect, there is provided a process for producing a polyurethane aerosol composition comprising reacting a polyol component comprising a polyol or thiol containing two isocyanate-reactive groups and a mixture comprising a diisocyanate to react with an isocyanate-terminated polyurethane prepolymer. Sequentially obtaining (i) an acidic water-solubilizing compound, (ii) a base for neutralizing the water-solubilizing compound, and (iii) a silyl end group. Providing a solubilized polyurethane prepolymer by reacting, dispersing the solubilized polyurethane prepolymer in water, reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender, and jetting Add the agent, polyurethane It includes obtaining an azole composition, and a method.

  In a sixth aspect, a method of providing a crosslinked polyurethane coating on a substrate from a one-part composition, the method comprising using a propellant through an aerosol actuator and an aqueous polyurethane dispersion on the substrate The aqueous polyurethane dispersion reacts (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water-solubilizing compound, and (iii) a diisocyanate. A method comprising: providing a crosslinked polyurethane coating by removing the water and condensing the silyl end group by removing the water and condensing the silyl end group. provide.

  In a seventh aspect, a polyurethane aerosol composition comprising a polymer, water and a dimethyl ether propellant, wherein the polymer comprises (i) a polyol or thiol having an isocyanate-reactive functional group, and (ii) neutralization A polymer obtained by reacting a water-solubilizing compound, (iii) a diisocyanate, and (iv) an isocyanate-reactive chain extender, wherein the polymer is from 10,000 g / mol to 200,000 g / mol. Compositions are provided having a weight average molecular weight in the range.

  In an eighth aspect, a method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition, the method comprising using a dimethyl ether propellant through an aerosol actuator and an aqueous polyurethane on the substrate Depositing the dispersion, wherein the aqueous polyurethane dispersion comprises (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water solubilizing compound, (iii) a diisocyanate, (iv) ) Comprising a polymer obtained by reacting with an isocyanate-reactive chain extender and removing water from the dispersion to cure the thermoplastic polyurethane coating, wherein the polymer is 10 Having a weight average molecular weight in the range of 1,000,000 g / mol to 200,000 g / mol. It includes, to provide a method.

Definitions As used herein,
“Diol” means a compound having exactly two hydroxyl functionalities;
“Diisocyanate” means a compound having exactly two isocyanate functionalities;
“Isocyanate” refers to a compound having a —N═C═O functional group,
“Polyol” refers to a compound having two or more hydroxyl functionalities;
“Polyurethane” generally refers to a polymer characterized by urethane and / or urea linkages;
“Thiol” refers to an organic sulfur compound having a —SH functional group,
“Urea” refers to a compound having a —NH ₂ CO (NH ₂ ) — chemical bond,
“Urethane” refers to a compound having a —NH—CO—O— chemical bond.

  As used herein, the terms “preferred” and “preferably” refer to embodiments described herein that may provide a particular effect under certain circumstances. However, other embodiments may be preferred in the same or other situations. Furthermore, references to one or more preferred embodiments do not imply that other embodiments are not useful and are not intended to exclude other embodiments from the scope of the invention. .

  As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a (a)” or “said / the / the” component may include one or more of the components and equivalents thereof known to those of skill in the art. Furthermore, the term “and / or” means one or all of the listed elements or combinations of any two or more of the listed elements.

  Throughout this specification “one embodiment”, “a particular embodiment”, “one or more embodiments”, or “an embodiment” refers to a particular feature, structure, It means that a material or property is included in at least one embodiment of the present invention. Accordingly, expressions such as “in one or more embodiments”, “in a particular embodiment”, “in one embodiment”, or “in an embodiment” appear in various places throughout this specification. Although not necessarily referring to the same embodiment of the present invention. Particular structures, materials, or properties may be combined in any suitable manner in one or more embodiments.

  In an exemplary embodiment, the provided polyurethane aerosol composition comprises a prepolymer having a urethane moiety and one or more silyl end groups, water, and optional additives (eg, rheology modifiers and / or antifoaming). Agent) and a propellant. These components are described in detail in the following chapters.

Polyurethane Prepolymers and Polymers The prepolymers described herein comprise a urethane portion comprising a portion derived from a polyisocyanate and a portion derived from a polyol and / or thiol, a neutralized anionic water solubilizing portion, Various, including a monovalent terminal silyl moiety, optionally a polyurea moiety derived from a bifunctional hydrazine or hydrazide chain extender, and a moiety derived from any (eg, polyol and / or amine) chain extender In addition to parts, it includes various other optional parts.

  In general, a silyl-terminated polyurethane dispersion is prepared by first obtaining a polyurethane prepolymer. In these embodiments, the prepolymer has at least one polyol or thiol component, at least one isocyanate-reactive water solubilizing component, at least one polyisocyanate (eg, diisocyanate) component, and optionally one. It is prepared from the above polyols and / or polyamine chain extenders. Optionally, the prepolymer is then neutralized and partially terminated with an alkoxysilane. In some embodiments, the resulting prepolymer is chain extended with a bifunctional hydrazide or hydrazine compound, in which case the remaining components have no hydrazide or hydrazine groups. The prepolymer may be dispersed in water before or after being chain extended with a bifunctional hydrazide or hydrazine compound. During hydrolysis, the alkoxysilane groups are then converted to -Si-OH chemical groups. When drying, the Si—OH groups condense to form siloxane bonds —Si—O—Si—.

  In another embodiment, polyurethane dispersions can be prepared that do not contain silyl end groups and therefore do not form covalently crosslinked networks after being sprayed onto a substrate. Nevertheless, these coatings can exhibit excellent properties, especially when preparing dispersions from polymers with sufficient high molecular weight.

  In a preferred embodiment, the polyurethane constituents are selected such that the polyurethane has little or no ethylene oxide units. The polyurethane may contain, for example, less than 1 weight percent (wt%) or less than 0.5 wt% ethylene oxide moieties.

  The polyurethane aerosol composition typically has a solids content ranging from about 5% to about 50% by weight, based on the total weight of the coated polyurethane (excluding the propellant). Next, the solid content may be adjusted based on the amount of water present in the dispersion. To obtain the desired solids content, the water is at least 50%, at least 60%, at least 65%, at least 67%, at least 70% by weight, based on the total weight of the composition excluding the propellant. Or in an amount of at least 73% by weight. Water may be present in an amount of up to 95 wt%, up to 90 wt%, up to 87 wt%, up to 85 wt%, or up to 82 wt%, based on the total weight of the composition excluding the propellant.

  Polyurethane compositions are generally formed from difunctional components (eg, diols, diisocyanates, hydrazines, dihydrazides, and diamines), but optionally multifunctional components having more than two functionalities May be incorporated into the polyurethane dispersion in limited amounts. When utilized, such multifunctional components provide branching. The urethane branching coefficient (“UBC”) may represent the total amount of branching provided by the polyfunctional polyisocyanate, polyol, and chain extender in the urethane portion of the silane terminated urethane dispersion. This coefficient excludes siloxane bonds such as -Si-O-Si- and -Si-OH, but includes other active hydrogen groups of silanes such as amines and mercaptans. Calculated assuming that unreacted isocyanate reacts with water. Using this measurement, UBC typically ranges from about 1.7 to about 2.25, preferably from about 1.85 to about 2.01. In some embodiments, the UBC is 2, meaning that all such components are difunctional (eg, diisocyanates and diols). Further embodiments of UBC are described in US Pat. No. 6,046,295 (Frisch et al.).

  The polyol component comprises a compound having two isocyanate-reactive functional groups (diol and derivatives thereof), and optionally a compound having more than two isocyanate-reactive groups (eg triol, tetrol, and derivatives thereof). In addition, each isocyanate-reactive group has at least one active hydrogen.

Isocyanate-reactive components such as polyols (eg, diols), thiols, and amines that can react with diisocyanates to prepare prepolymers can be divided into two groups: high molecular weight compounds and low molecular weight compounds. The high molecular weight compound may have an average molecular weight of at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1000 g / mol. In some embodiments, the high molecular weight compound has an average molecular weight of up to 9,000, up to 8,000, up to 7,000, up to 6,000, or up to 5,000 g / mol. Low molecular weight compounds (chain extenders) can have an average molecular weight of up to 400, up to 350, up to 300, or up to 250 g / mol. Optionally, the aforementioned average molecular weight is a weight average molecular weight (M _w ).

  Examples of high molecular weight compounds are polyester polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides, and polyhydroxy polythioethers. Polyester polyols and especially polyether polyols may be preferred.

  Suitable polyester polyols include reaction products of polyhydric, preferably dihydric alcohols, to which trihydric alcohols may be added, and polybasic, preferably dibasic carboxylic acids. Instead of these polycarboxylic acids, the corresponding carboxylic acid anhydrides or polycarboxylic acid esters of lower alcohols, or mixtures thereof may be used to prepare the polyester. The polycarboxylic acid may be aliphatic, alicyclic, aromatic, and / or heterocyclic, eg, may be substituted with a halogen atom and / or contain ethylenic unsaturation. Also good. The following is mentioned as an example. Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endo Methylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer and trimer fatty acids that can be mixed with monomeric fatty acids such as oleic acid, dimethyl terephthalate and bisglycol terephthalate. Lactone polyesters may also be used. An exemplary fatty acid dimer diol is available from Croda International (Snaith, UK) under the trade name PRIPOL 2033. Dimer polyester polyols based on fatty acids are available from the same supplier under the trade name “PRIPLAST 1838”.

  In some embodiments, the polyurethane is prepared from an aliphatic polyester diol. Optionally, the aliphatic polyester diol can be the main or only high molecular weight diol of the polyurethane.

  Suitable polyhydric alcohols that can be used in the preparation of polyester polyols and that may also be useful as low molecular weight polyol chain extenders include, for example, ethylene glycol, diethylene glycol, (1,2 or 1,3) propylene diol, ( 1,4 or 1,3) butanediol, (1,6) hexanediol, (1,8) octanediol, neopentyl glycol, (1,4) cyclohexanedimethanol, bis (2-hydroxyethyl) hydroquinone (HQEE) ), 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, dipropylene glycol, dibutylene glycol Polybutylene glycol, glycerine, and trimethylolpropane. Various mixtures of low molecular weight polyol chain extenders may be utilized.

In some embodiments, the polyurethane comprises an alicyclic chain extender moiety, particularly a cyclohexane moiety. In another embodiment, the polyurethane comprises an aliphatic C ₃ -C ₆ alkylene diol chain extender, for example, the butane diol. When utilized, the concentration of the polyol chain extender is typically at least 0.1, 0.2, or 0.3% by weight, based on the total weight of the polyurethane, up to 5, 6, 7, It can be 8, 9, or 10% by weight.

  Polycarbonates containing hydroxyl groups include diols (eg, propanediol- (1,3), butanediol- (1,4), and / or hexanediol- (1,6), diethylene glycol, triethylene glycol, or Tetraethylene glycol) and the products obtained from the reaction of phosgene, diaryl carbonate (eg diphenyl carbonate) or cyclic carbonate (eg ethylene or propylene carbonate). Moreover, the polyester carbonate obtained from the above-mentioned polyester or polylactone and phosgene, diaryl carbonate, or cyclic carbonate is also suitable.

  In some embodiments, the polyurethane is prepared from a polycarbonate diol. Optionally, the polycarbonate diol is the main or only high molecular weight diol of the polyurethane.

  Suitable polyether polyols are obtained by reaction of starting compounds containing reactive hydrogen atoms with alkylene oxides such as propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin or mixtures of these alkylene oxides. be able to. Suitable starting compounds containing reactive hydrogen atoms include polyhydric alcohols described for the preparation of polyester polyols, water, methanol, ethanol, 1,2,6-hexanetriol, 1,2,4-butanetriol. , Trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycoside, sucrose, phenol, isononylphenol, resorcinol, hydroquinone, 1,1,1- or 1,1,2-tris- (hydroxyphenyl) -ethane .

  In some embodiments, the polyurethane is prepared from propylene oxide and / or butylene oxide polyether diol. The propylene oxide and / or butylene oxide polyether diol can be the main or only high molecular weight diol of the polyurethane.

  In some embodiments, the high molecular weight diol (s) is at least 30%, at least 35%, at least 40%, at least 45%, or at least based on the total weight of the polyurethane prior to hydrolysis. Present in an amount of 50% by weight. In some embodiments, the high molecular weight diol is generally in an amount of 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less, based on the total weight of the polyurethane prior to hydrolysis. Used in In an exemplary embodiment, the polyurethane includes a urethane moiety derived from a high molecular weight diol moiety. The high molecular weight diol moiety can be present in the hydrolyzed polyurethane in approximately the same compositional range as described immediately above.

  In addition to the difunctional components described above, a small amount of branching (as already described) is utilized using small amounts of trifunctional or higher functional components commonly known in polyurethane chemistry such as trimethylolpropane. ) Can be obtained. Low concentrations of monofunctional end-protected isocyanate-reactive components (eg monools and monoamines) may be used at low concentrations, but use little or no monofunctional component other than monofunctional alkoxysilane compounds It is generally preferred not to. Polyurethanes typically contain 0% by weight, alternatively up to 1% by weight or up to 0.5% by weight of monofunctional end-protected isocyanate-reactive components other than alkoxysilane compounds.

  The polyisocyanate component includes a compound having two isocyanate groups (diisocyanate and / or an adduct thereof). The polyisocyanate component may optionally include compounds having more than 2 isocyanate groups (eg, triisocyanates and / or adducts thereof) to introduce branching as previously described. As defined herein, an adduct of a polyisocyanate compound refers to an isocyanate functional derivative of a polyisocyanate compound and a polyisocyanate prepolymer. Examples of adducts include, but are not limited to, isocyanate compounds selected from the group consisting of urea, biuret, allophanate, dimers and trimers, uretonimediones, and mixtures thereof. Any suitable organic polyisocyanate such as an aliphatic, cycloaliphatic, araliphatic, or aromatic polyisocyanate may be used, either alone or as a mixture of two or more.

  Aromatic polyisocyanates can be more reactive towards polyols and other poly (active hydrogen) compounds than aliphatic polyisocyanates. Suitable aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dimer of toluene diisocyanate (available from Bayer AG (Leverkusen, Germany) under the trade name DESMODUR TT), diphenylmethane 4, Examples include, but are not limited to, those selected from the group consisting of 4'-diisocyanate, 1,5-diisocyanato-naphthalene, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, and mixtures thereof.

Advantageously, aliphatic isocyanates can provide better light stability than aromatic compounds. Examples of useful alicyclic polyisocyanates include dicyclohexylmethane diisocyanate (H ₁₂ MDI, manufactured by Bayer AG, commercially available as DESMODUR W), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), 1,4- Examples include, but are not limited to, those selected from the group consisting of cyclohexane bis (methylene isocyanate) (BDI), 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI), and mixtures thereof. Examples of useful linear or branched aliphatic polyisocyanates include hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI), Those selected from the group consisting of 2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, dimer diisocyanate, urea of hexamethyl diisocyanate, and mixtures thereof. However, it is not limited to these.

In some embodiments, the diisocyanate component includes a cycloaliphatic moiety, such as a dicyclohexylmethane moiety, as may be derived from H ₁₂ MDI and its derivatives. Other cycloaliphatic moieties include alkylcyclohexyl as may be derived from IPDI. A mixture of alicyclic moieties may be present.

  In some embodiments, the cycloaliphatic diisocyanate (s) is generally at least 15 wt%, at least 20 wt%, or at least 25 wt%, based on the total weight of the polyurethane prior to hydrolysis, and Typically, it is utilized in an amount of up to 50%, up to 45%, up to 40%, or up to 35% by weight. Thus, the polyurethane includes a urethane portion derived from a cycloaliphatic diisocyanate. Cycloaliphatic (eg, diisocyanate) moieties are present in the hydrolyzed polyurethane in approximately the same compositional range as described immediately above.

  The polyurethane prepolymer can be characterized as an isocyanate-terminated polyurethane prepolymer. The isocyanate groups of the isocyanate-terminated polyurethane prepolymer are utilized in subsequent reactions.

The polyurethane prepolymer preferably has an excess of isocyanate, i.e., an isocyanate-reactive component (e.g., a polyol component), an anionic water-solubilizing compound, an alkoxysilane compound, and other isocyanate-reactive compounds in the prepolymer. For each active hydrogen radical that contributes, it is prepared with an isocyanate containing more than one isocyanate radical in the reaction mixture. “Active hydrogen” is a nucleophilic hydrogen atom that conforms to the Zerevitinov determination of a hydrogen atom (a compound that produces methane when reacted with a purified n-butyl ether solution of methylmagnesium iodide). Isocyanate-reactive groups having at least one active hydrogen include hydroxyl groups (—OH), thiol groups (—SH), and amines [—NH _{2 and} —NHR, wherein R is phenyl, about 1 to about Selected from the group consisting of linear or branched aliphatic groups containing 12 carbon atoms, and alicyclic groups)].

  Suitable polyurethane prepolymers preferably have a ratio of isocyanate equivalents to active hydrogen equivalents in the range of 1: 1 (eg, 1.05: 1) to greater than 4: 1. In some embodiments, the ratio is up to 3: 1 or up to 2: 1. This ratio is highest after the polyol component has reacted with the isocyanate component and then decreases with the addition of the isocyanate-reactive component.

  The isocyanate terminated polyurethane prepolymer reacts with the anionic water solubilizing compound. The water solubilizing compound includes at least one anionic water solubilizing group and at least one isocyanate-reactive functional group. In some embodiments, each compound has two isocyanate-reactive groups that are linked to each other and to an anionic water-solubilizing group through organic radicals. Suitable anionic water solubilizing groups include carboxyl, sulfate, sulfonate, phosphate, and the like, which ionize in water when combined with the corresponding neutralizing (eg, salt-forming) compound.

Suitable anionic water solubilizing compounds are those of the formula (HB) ₂ R ¹ A wherein A is an anionic water solubilizing moiety and B is O, S, NH or NR (where R Is an alkyl group containing 1 to 4 carbon atoms) and R ¹ has a valence of at least 3 and is typically a trivalent organic linkage containing 2 to 25 carbon atoms Represents a group]. Exemplary anionic water solubilizing compounds can be found in US Pat. No. 7,091,280 (Rische et al.).

Optionally, A is —OSO ₃ M, —CO ₂ M, —OPO (OM) ₂ , where M is H or one equivalent of a monovalent or divalent soluble cation such as sodium, potassium, or calcium. An anionic group. Exemplary anionic water solubilizing compounds include dihydroxy carboxylic acid, dihydroxy sulfonic acid, dihydroxy phosphonic acid, and salts thereof, such as dimethylolpropionic acid shown as follows.

  The amount of anionic water solubilizing group is preferably sufficient to emulsify the polyurethane polymer in water. In some embodiments, the weight ratio of isocyanate groups to anionic water solubilizing groups is at least 3: 1, at least 4: 1, at least 5: 1, or at least 6: 1, and typically 15: 1 or less, or 10: 1 or less. In some embodiments, the anionic water solubilizing compound is at least 1 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt%, based on the total weight of the polyurethane before hydrolysis. %, And typically up to 5% by weight. Thus, the polyurethane includes a urethane portion derived from one or more anionic water solubilizing compounds. The anionic water solubilizing moiety is present in the hydrolyzed polyurethane in approximately the same compositional range as described immediately above.

  In a preferred embodiment, the anionic groups of the anionic water solubilizing compound are neutralized prior to reacting the isocyanate-terminated polyurethane prepolymer with the isocyanate-reactive silane compound. A sufficient amount of base or neutralizing compound can be used to stabilize the dispersion anionic, eg, by forming a salt with a pendant (eg, carboxylate) water solubilizing group in the resulting polyurethane. . Examples of useful salt-forming compounds include ammonia, alkylamines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triethanolamine, and any mixture thereof, It is not limited to these.

  In a preferred embodiment, at least some of the isocyanate groups of the isocyanate-terminated polyurethane prepolymer react with the isocyanate-reactive silane compound. Silane compounds containing one, two or three hydrolyzable groups on silicon and one organic group containing isocyanate-reactive groups. Alkoxy groups are the most typical hydrolyzable groups.

In some embodiments, the alkoxysilane compound has the formula (R ² O) ₃ SiR ³ —Z, wherein R ² is independently hydrogen or C ₁ -C ₄ alkyl (eg, a methoxy or ethoxy group R ³ is a divalent group selected from alkylene, alkylarylene (eg, alkylphenyl group), and oxyalkylene, and Z is —OH, —SH, —NHR ⁴ , And —NH ₂ , wherein R ⁴ is selected from the group consisting of an aromatic or aliphatic cyclic group. When R ³ is alkylene or oxyalkylene, the group may be linear, branched, or cyclic. An alkylene or oxyalkylene group typically contains 1 to 12 carbon atoms, and in some embodiments, 2 to 3 carbon atoms.

  Examples of suitable aminoalkylenealkoxysilanes include 2-aminoethyl-dimethylmethoxysilane, 6-aminohexyl-tributoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-amino Mention may be made of propyl-methylditriethoxysilane, 5-aminopentyl-trimethoxysilane, 5-aminopentyl-triethoxysilane, and 3-aminopropyl-triisopropoxysilane. Examples of other isocyanate-reactive alkoxysilanes include hydroxylmethyl-triethoxysilane and 3-mercaptopropyltriethoxysilane.

  In some embodiments, the alkoxysilane compound (s) is at least 0.1, at least 0.2, at least 0.3, at least 0.4, or at least based on the total weight of the polyurethane prior to hydrolysis. 0.5% by weight, and in some embodiments, is utilized in amounts up to 7, up to 8, up to 9, or up to 10% by weight. Thus, the polyurethane includes a urethane portion derived from one or more alkoxysilane compounds. The alkoxysilane moiety is present in the polyurethane in the same compositional range as described immediately before hydrolysis and is slightly reduced after hydrolysis due to the conversion of alkoxy groups to —OH. The silicon atom concentration can generally range from 0.015 to 1.5% by weight of the polyurethane.

Some of the isocyanate groups of the isocyanate-terminated polyurethane prepolymer can be chain extended with a bifunctional hydrazine or hydrazide compound. The bifunctional hydrazine compounds, in addition to anhydrous hydrazine having the formula H _{2 N-NH 2,} typically include hydrazine hydrate 50 to 60% of the hydrazine.

  Examples of the dihydrazide include carbodihydrazide (CDH), oxalic acid dihydrazide, and thiocarbohydrazide, which are shown below.

並びに、以下の式を有するジヒドラジドが挙げられる。

Also included are dihydrazides having the following formula:

［式中、Ｒは、共有結合（例えば、シュウ酸ジヒドラジドの場合、窒素等のヘテロ原子（例えば、イミドジカルボン酸ジヒドラジドの場合）又は多価（例えば、二価）有機ラジカル、例えば、任意に酸素又は窒素等の隣接するヘテロ原子を含む（例えば、Ｃ_１〜Ｃ_１８）アルキレン、典型的には、５００、４００、又は３００ｇ／モル以下の重量平均分子量を有するアリーレン（例えば、フェニル）である］。幾つかの例示的なジヒドラジドを以下の通り示す。

[Wherein R is a covalent bond (eg, in the case of oxalic acid dihydrazide, a heteroatom such as nitrogen (eg, in the case of imidodicarboxylic acid dihydrazide)) or a polyvalent (eg, divalent) organic radical, eg, optionally oxygen Or an alkylene containing adjacent heteroatoms such as nitrogen (eg, C ₁ -C ₁₈ ), typically an arylene having a weight average molecular weight of 500, 400, or 300 g / mol or less (eg, phenyl)] Some exemplary dihydrazides are shown as follows.

  In some embodiments, the hydrazine and / or dihydrazide compound (s) is at least 0.1, at least 0.2, at least 0.3, at least 0.4, based on the total weight of the polyurethane prior to hydrolysis. Or in an amount of at least 0.5% by weight, and in some embodiments, in an amount of up to 5, up to 6, up to 7, up to 8, up to 9, or up to 10% by weight. Accordingly, in these embodiments, the polyurethane comprises urea moieties derived from hydrazine and / or dihydrazide compounds. The hydrazine and / or dihydrazide moieties are present in the hydrolyzed polyurethane in approximately the same compositional range as described immediately above.

  In some embodiments, the isocyanate-terminated polyurethane prepolymer is augmented with a polyfunctional (eg, difunctional) amine chain extender. Examples of useful diamine chain extenders include 4,4′-methylenebis (o-chloroaniline), 2,5-diethyl-2,4-toluenediamine, 4,4′-methylenebis (3-chloro-2, 6-diethylaniline), propylene glycol bis (4,4′-aminobenzoate), 3,5-di (thiomethyl) -2,4-toluenediamine, methylenebis (4,4′-aniline), ethyl-1,2 -Di (2-aminothiophenol), 4-chloro-3,5-diaminoisobutylbenzoate, 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, N, N'-dialkyl (Methylenedianiline), N, N′-dialkyl (1,4-diaminobenzene), and those selected from the group consisting of these, But it is not limited to these.

  In some embodiments, the multifunctional amine, particularly the diamine (s) chain extender, is at least 0.1, at least 0.2, at least 0.3, based on the total weight of the polyurethane prior to hydrolysis. Present in an amount of at least 0.4, or at least 0.5% by weight, and in some embodiments, up to 5, up to 6, up to 7, up to 8, up to 9, or up to 10% by weight. In some embodiments, the multifunctional amine (eg, diamine) is utilized in an amount of at least 1.0, at least 1.5, or at least 2% by weight. Thus, the polyurethane includes urea moieties derived from multifunctional amines (eg, diamines). The polyfunctional amine (eg, diamine) moiety is present in the hydrolyzed polyurethane in approximately the same compositional range as described immediately above.

  The polyurethane prepolymer composition is typically prepared using a catalyst according to methods known in the art. The amount of catalyst may be increased to about 0.5 parts by weight of the isocyanate-terminated prepolymer. In some embodiments, the amount of catalyst ranges from about 0.005 to about 0.05 parts by weight. Examples of useful catalysts include tin II and tin IV salts such as stannous octoate and dibutyltin dilaurate, and tertiary amine compounds such as dibutyltin diacetate, triethylamine and bis (dimethylaminoethyl) ether, β, β -Those selected from the group consisting of morpholine compounds such as dimorpholinodiethyl ether, bismuth carboxylate, zinc-bismuth carboxylate, iron (III) chloride, potassium octoate, and potassium acetate, but are not limited thereto. .

  A solvent can be utilized to control the viscosity of the isocyanate-terminated prepolymer. Examples of useful solvents (often volatile organic compounds) added for this purpose include ketones (eg methyl ethyl ketone, acetone), tertiary alcohols, ethers, esters, amides, hydrocarbons, chloro Hydrocarbons, chlorocarbons, and mixtures thereof include but are not limited to these. Such a solvent is usually removed at the end of the reaction by vacuum heating. Under laboratory conditions, the solvent can be removed using a Haake Roto evaporator or other similar apparatus.

  It is also possible to use a solvent to promote coalescence of the silyl-terminated polyurethane particles in the dispersion to form a continuous film. Examples of such coalescing solvents for use in dispersions include n-methylpyrrolidinone (NMP), n-butyl acetate, dimethylformamide, toluene, methoxypropanol acetate (PM acetate), dimethyl sulfoxide (DMSO), ketone , Alcohol, dimethylacetamide, and mixtures thereof, but are not limited to.

Isocyanate-terminated polyurethane prepolymers are prepared in a sequential process. In a reactor equipped with a stirrer, heater, and dry gas purge (eg, nitrogen or argon, eg), the (eg, high molecular weight) polyol and polyisocyanate components are added to any catalyst and any solvent (eg, 0.05 With anhydrous methyl ethyl ketone with a concentration of H ₂ O of less than%). The reactor is heated to the reaction temperature (typically above 75 ° C. and up to about 100 ° C.) and the reaction is allowed to proceed for a period of time. This time is 15 minutes to 8 hours, preferably 30 minutes to 4 hours. Next, an isocyanate-reactive anionic water-solubilizing component (eg, dimethylolpropionic acid) is added with any solvent and the reaction is allowed to proceed for a period of time. This time is from 15 minutes to 8 hours, preferably from 1 hour to 6 hours, while keeping the reaction exotherm below 100 ° C. to minimize unwanted side reactions. Optionally, all or part of the (eg, polyol) chain extender component may be added at this point along with any solvent and the reaction is allowed to proceed for a period of time. This time is 15 minutes to 8 hours, preferably 1 hour to 4 hours. The viscosity of the prepolymer is typically low enough to facilitate the dispersion process (about 70,000 cps or less).

  The next step is to combine the isocyanate-terminated prepolymer with a neutralizing compound (eg, triethylamine) and subsequently react some of the isocyanate groups of the prepolymer with an isocyanate-reactive alkoxysilane compound. Bifunctional hydrazine or hydrazide compounds may be used to form at least a portion of the prepolymer to form a polymer. The reaction of the prepolymer with the hydrazine or hydrazide compound can occur before or after the prepolymer is dispersed in water. Optionally, a chain extender such as alkylene diamine may be added to react with some of the remaining isocyanate groups. In one embodiment, an optional second alkylene diamine is added after the hydrazine / hydrazide compound is reacted before the prepolymer is dispersed in water and a dispersion is formed.

  After hydrolysis, the alkoxysilane group is converted to a Si—OH group that can be cured through a condensation reaction to form a siloxane bond having the formula —Si—O—Si—. Thus, the polyurethane prepolymer component represents the base material of the covalently linked crosslinked network. These cross-linked materials can exhibit enhanced moisture resistance, as evidenced by improved optical clarity when the polyurethane film is exposed to a humid or humid environment immediately after curing.

Solvent In an exemplary embodiment, the aforementioned polymer is dispersed in water to obtain an aqueous composition having a suitable viscosity that can be properly sprayed onto a substrate to form a film.

  In one process, the polymer or prepolymer is additionally added undiluted or in solution to most or a substantial portion of the aqueous dispersion medium with stirring. Alternatively, the aqueous dispersion medium may be additionally added to the prepolymer with stirring. This latter method is less preferred because, in general, a high viscosity grease-like material is obtained when the dispersion medium is first added, which is difficult to mix with the chain extender. This is because it can be. Without efficient stirring, the possibility of forming an unstable emulsion system due to agglomerates with large particle sizes increases. By adding the prepolymer to water, this high initial viscosity is avoided.

  As described in US Pat. Nos. 4,147,679 (Scriven et al.) And 4,066,591 (Scriven et al.), If the solvent is added to the aqueous medium, it is added before or after the prepolymer is added. May be added to the isocyanate-containing prepolymer, or even to the polymer. Reference to an aqueous dispersion medium is intended to include water and water with a solvent and optionally a neutralizing agent. When water is added to the prepolymer, any method known to those skilled in the art in making aqueous polyurethane dispersions can be used to reduce the likelihood of increasing the formation of large particle size agglomerates.

Optional Additives Various polyurethane dispersion additives are known in the art. In some embodiments, one or more of these additives are added to the disclosed polyurethane aerosol composition.

  The polyurethane aerosol composition optionally includes at least one rheology modifier, such as a thickener. Thickeners are additives that increase the viscosity of a liquid, solution, or mixture without substantially changing other properties. In order to provide a uniform spray coating, a suitable thickener must quickly increase the viscosity of the coating composition when the propellant volatilizes and adheres the coating to a vertical surface without dripping. I have to let it. Advantageous thickeners include those based on urethane block copolymers. Particularly preferred thickening agents include those based on hydrophobically modified ethylene oxide urethane block copolymers, such as those available from Dow Chemical Company (Midland, MI) under the trade name ACRYSOL.

  Preferably, the amount of rheology modifier present is sufficient to allow the polyurethane dispersion to adhere to an acceptable vertical extent when sprayed onto the substrate. In some embodiments, the rheology modifier is at least 0.1 wt%, at least 0.375 wt%, at least 0.5 wt%, at least 0.75 wt%, at least based on the total weight of the composition It is present in an amount of 1 wt%, at least 1.1 wt%, or at least 1.2 wt%. In some embodiments, the rheology modifier is up to 5%, up to 4.5%, up to 4%, up to 3.5%, up to 3% by weight, based on the total weight of the composition. Or present in an amount up to 2.25% by weight. In a preferred method, a rheology modifier is added to the water before dispersing the isocyanate-terminated polyurethane prepolymer synthesized above.

  Optionally, the polyurethane aerosol composition comprises at least one antifoaming agent. Antifoaming agents are chemical additives that prevent foam formation before or after the dispersion is sprayed onto the substrate. These additives are particularly beneficial in aerosol-based coatings because the presence of foam can cause surface defects and / or impair spray performance. Particularly useful antifoaming agents include modified polyols such as Elementis Specialties, Inc. (East Windsor, NJ) can be obtained under the trade name DAPRO.

  The amount of antifoam agent should ideally be sufficient to eliminate or minimize foam related defects in the coated polyurethane film. In some embodiments, the antifoaming agent is at least 0.01 wt%, at least 0.05 wt%, at least 0.075 wt%, at least 0.1 wt%, at least based on the total weight of the composition It is present in an amount of 0.12 wt%, or at least 0.15 wt%. In some embodiments, the antifoaming agent is up to 1.2%, up to 1%, up to 0.8%, up to 0.75%, up to 0.00%, based on the total weight of the composition. It is present in an amount of 65% by weight, or up to 0.6% by weight.

  Many other additives may be included. These additives include, for example, crosslinking agents, plasticizers, thixotropic agents, biocides, adhesion promoters (eg, silane adhesion promoters), corrosion inhibitors, binders, crater inhibitors, slip aids, filling Agents, flow aids, pigments, colorants, light stabilizers (eg, hindered amine light stabilizers and UV absorbers), antioxidants, and antifouling agents, but are not limited thereto. For example, the polyurethane aerosol composition may include agents such as pigments or colorants to color when applied to a glass substrate. In one exemplary embodiment, the polyurethane aerosol composition comprises a colorant that is photoactive, as described in International Patent Application WO2013 / 003404 (Endle et al.).

Propellant An aerosol composition propellant is used to eject polymer, water, and optional additives from a container. Generally, the propellant is a liquefied gas, a compressed gas, or both.

  The polyurethane aerosol composition may comprise any of a number of liquefied gases known to those skilled in the art as propellants. Examples of such a liquefied gas include dimethyl ether, C1-C4 alkanes (for example, propane, butane, isobutane, cyclobutane, and mixtures thereof), refrigerants, hydrochlorofluorocarbons, hydrofluorocarbons, and mixtures thereof. Examples of the compressed gas include carbon dioxide, nitrogen, nitrous oxide, compressed air, and a mixture thereof. Although there is no particular restriction on the choice of propellant, it has been found that a preferred aqueous polyurethane aerosol composition comprises dimethyl ether, which results in a film having surprisingly high optical clarity.

  In some embodiments, the propellant is at least 10%, at least 11%, at least 12%, at least 13%, at least 14%, at least 15%, based on the total weight of the composition, It is present in an amount of at least 16%, at least 17%, at least 18%, at least 19%, or at least 20%. In some embodiments, the propellant is up to 40, up to 35, up to 34, up to 33, up to 32, up to 31, up to 30, up to 29, up to 28, up to 27, based on the total weight of the composition. Present in an amount of up to 26, up to 25, up to 24, up to 23, up to 22, up to 21, or up to 20% by weight.

Apparatus and Application The provided polyurethane aerosol composition and propellant can be filled into a hermetically sealed container as part of an aerosol apparatus known to those skilled in the art. Such aerosol devices typically include a hermetically sealed container, along with suitable valves and actuators that allow the user to discharge the contents of the container in a controlled manner. Exemplary actuators include, for example, Aptar Group Inc (Chicago, IL), Lindal Valve Co. (Bedfordshire, England), Newman-Green Inc. (Addison, IL), Precision Valve Co. (Yonkers, NY), and Summit Packaging Systems, Inc. (Manchester, NH).

  To use the aerosol device, the user points the actuator orifice toward the substrate to be coated and depresses the actuator to release a portion of the pressurized contents of the container, thereby releasing the polyurethane composition into the container. It can be sprayed onto the substrate. The spray may be a mist-like pattern, a saddle pattern, or a flow pattern. The fog-like pattern is characterized by fine droplets that coalesce, form a smooth, continuous, and optionally transparent film. The saddle pattern is characterized by large droplets that can form a smooth film with or without coalescence. The flow pattern is characterized by a narrow continuous flow that forms a continuous film without coalescence. In general, a fog-like pattern is preferred to form a smooth continuous film. The saddle and flow patterns may be desirable for other applications. The composition of the composition that coats the substrate generally reflects the polyurethane aerosol composition, except most if not all of the propellant that volatilizes before reaching the substrate.

  One aspect of the invention relates to an aerosol polyurethane composition that is shelf stable for at least one year and optionally crosslinkable at room temperature. Once sealed in the container, these compositions were observed to spray on the substrate and cure or solidify as designed over a period of more than one year from the time the composition was first placed. In contrast, conventional crosslinkable systems, such as those based on aziridine, have been found to polymerize early (in an aerosol container) within a much shorter period of time, typically within a few days. It was. Such compositions are described, for example, in Coogan, Richard G. et al. (1997). Post-crosslinking of water-bone ureanes. Progress in Organic Coatings, 32, 51-63.

The polyurethane of the aerosol composition has a weight average molecular weight (M) of at least 10,000, at least 14,000, at least 20,000, at least 30,000, at least 40,000, at least 45,000, or at least 50,000 g / mol. _w ). In exemplary embodiments, the polyurethane has a weight average molecular weight of up to 200,000, up to 175,000, up to 150,000, up to 125,000, up to 100,000, or up to 75,000 g / mol.

  As already suggested, polyurethane polymers contain reactive silanol (Si—OH) groups that can react with each other under suitable conditions to form siloxane bonds —Si—O—Si—. Assuming that the silyl end groups are multifunctional, this can produce a highly crosslinked polyurethane network. This reaction can be facilitated by removing water after coating the substrate, condensing silanol groups, and crosslinking the system.

  Advantageously, it has been observed that the coated polyurethane is resistant to degradation by heat and ultraviolet light. This can be measured by the change in gloss and / or color of the film. Preferably, these coatings exhibit a color change ΔE value of less than 1 (after 3200 hour weathering test as described in the examples), more preferably less than 0.5. In some embodiments, the color change ΔE is less than 0.25. Preferably, these coatings exhibit a gloss reduction% of less than 12%, more preferably less than 8% (after 3200 hour weathering test as described in the examples). In some embodiments, the% gloss reduction is less than 4% or less than 2%.

  In other embodiments, the polyurethane polymers described herein have water resistance (determined by the test method in the examples) as evidenced by a ΔE value of less than 20, more preferably less than 10. In some embodiments, the water resistance ΔE is less than 8, less than 5, less than 3, or less than 2.

  The dispersion of the present invention is spray-coated on various substrates and has high gloss, water and solvent resistance, toughness, scratch resistance, and preferably heat and light stability. A film that does not turn yellow can be formed. Leather, woven and non-woven webs, vinyl, glass, glass fiber, wood, metal, primed and painted metals and other treated metals (eg, automotive and marine surfaces), polymeric materials and surfaces, etc. It can be coated with the polyurethane coating described in the specification.

  In some embodiments, provided polyurethane coatings are useful as outermost or intermediate coatings. Advantageously, these coatings can be optically transparent to avoid changing the aesthetic appearance of the underlying layer or substrate. For example, these coatings are primer layers on metal (including primed and painted metals), plastic, and fiber reinforced plastic composite substrates used in the production of vehicle body parts and electrical enclosures. And may be applied to the entire sealer layer. Examples of the main body of the vehicle include a bonnet, a fender, a bumper, a grill, and a rocker panel. Examples of the housing of the electric product include a washing machine, a clothes dryer, and a refrigerator. Vehicles that can benefit from these coatings include cars, trucks, bicycles, aircraft, and ships.

  The coating typically includes paint, enamel, and lacquer and is applied under the topcoat / finish coating that can itself be chemically crosslinked to provide a durable, scratch-resistant surface finish. It may be used as an intermediate coating. The composition of the present invention can also adhere to a body filler composition used in the repair of automobile bodies.

  Also provided aerosol compositions include glass, boron, graphite, ceramic, fiber reinforced plastics reinforced by the addition of different polymer fibers, and inorganic powders (eg, calcium carbonate, talc, titanium dioxide, carbon black, etc.) , Flakes (eg, aluminum or mica), and composites, such as filled plastics, whose plastic properties have been altered by the addition of microspheres / beads (eg, glass or polymer). Further, the composition of the present invention may be coated on the surface of concrete, asphalt or the like (including roads, courtyards, and sidewalks) or a back surface-adhesive road marking tape.

The provided compositions and methods can be further illustrated through the following non-exhaustive list of embodiments A-BL.
A. A polyurethane aerosol composition comprising a polymer, water and a propellant, wherein the polymer comprises (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water solubilizing compound, A polyurethane aerosol composition, which is a polymer obtained by reacting iii) diisocyanate with (iv) an isocyanate-reactive chain extender comprising hydrazine or hydrazide.
B. The composition of Embodiment A wherein the polymer has a weight average molecular weight in the range of 10,000 g / mol to 200,000 g / mol.
C. The composition of Embodiment B wherein the polymer has a weight average molecular weight in the range of 14,000 g / mol to 75,000 g / mol.
D. A polyurethane aerosol composition comprising a urethane portion, a silyl end group, water and a propellant, wherein the urethane portion is (i) a polyol or thiol having an isocyanate-reactive functional group, and (ii) neutralized water. A polyurethane aerosol composition, which is a urethane moiety obtained by reacting a solubilizing compound with (iii) diisocyanate.
E. The composition of Embodiment D wherein the silyl end group comprises an alkoxysilane having the formula:
_{^{(R 2 O) 3 SiR 3}} -Z
Wherein R ² is hydrogen or C ₁ -C ₄ alkyl, R ³ is divalent alkylene, alkylarylene, oxyalkylene, Z is —OH, —SH, —NHR ⁴ , and —NH ₂ (wherein R ⁴ is an aromatic or aliphatic cyclic group)].
F. The composition according to any one of embodiments AE and BE-BG, wherein the neutralized water solubilizing compound comprises a reaction product of the following formula:
(HB) ₂ R ¹ A
[Wherein B is O, S, NH, or NR (wherein R is an alkyl group containing 1 to 4 carbon atoms), and R ₁ is a trivalent organic linking group. , A is an anionic group selected from —SO ₃ M, —OSO ₃ M, —CO ₂ M, and —OPO (OM) ₂ , where M is a water-soluble cation].
G. Embodiments A to F and BE to BG wherein the water is present in an amount ranging from 50% to 90% by weight, based on the total weight of the composition excluding the propellant. Composition.
H. The composition of embodiment G, wherein the water is present in an amount ranging from 70% to 85% by weight, based on the total weight of the composition excluding the propellant.
I. The composition of Embodiment H wherein the water is present in an amount ranging from 73% to 82% by weight, based on the total weight of the composition excluding the propellant.
J. et al. The composition according to any one of embodiments AI and BE-BG, wherein the propellant is present in an amount ranging from 10 to 40% by weight, based on the total weight of the composition.
K. The composition of Embodiment J, wherein the propellant is present in an amount ranging from 12 to 35% by weight, based on the total weight of the composition.
L. The composition according to embodiment K, wherein the propellant is present in an amount ranging from 20 to 30% by weight, based on the total weight of the composition.
M.M. The composition according to any one of embodiments A to L, wherein the propellant comprises dimethyl ether.
N. The composition of any one of Embodiments AM, wherein the polyurethane component of the composition has up to 1 wt% ethylene oxide.
O. The composition according to embodiment D or E, further comprising a urea moiety obtained by reacting an isocyanate-terminated prepolymer with an isocyanate-reactive chain extender.
P. The composition according to embodiment O or BE, wherein the isocyanate-reactive chain extender is hydrazine or hydrazide.
Q. The composition according to embodiment P, wherein the hydrazide is selected from carbodihydrazide, oxalic dihydrazide, thiocarbohydrazide, or dihydrazide having the formula:

（式中、Ｒは、共有結合、ヘテロ原子、又は二価有機ラジカルである）。
Ｒ．レオロジー調整剤を更に含む、実施形態Ａ〜Ｑ及びＢＥ〜ＢＧのいずれか１つに記載の組成物。
Ｓ．前記レオロジー調整剤が、ウレタンブロック共重合体を含む増粘剤である、実施形態Ｒに記載の組成物。
Ｔ．前記ウレタンブロック共重合体が、疎水変性エチレンオキシド系ウレタンブロック共重合体である、実施形態Ｓに記載の組成物。
Ｕ．前記レオロジー調整剤が、前記組成物の全重量に基づいて、０．１〜５重量％の範囲の量で存在する、実施形態Ｒ〜Ｔのいずれか１つに記載の組成物。
Ｖ．前記レオロジー調整剤が、前記組成物の全重量に基づいて、０．３７５〜３重量％の範囲の量で存在する、実施形態Ｕに記載の組成物。
Ｗ．前記レオロジー調整剤が、前記組成物の全重量に基づいて、０．７５〜２．２５重量％の範囲の量で存在する、実施形態Ｖに記載の組成物。
Ｘ．消泡剤を更に含む、実施形態Ａ〜Ｗ及びＢＥ〜ＢＧのいずれか１つに記載の組成物。
Ｙ．前記消泡剤が、変性ポリオールを含む、実施形態Ｘに記載の組成物。
Ｚ．前記消泡剤が、前記組成物の全重量に基づいて、０．０１〜１．２重量％の範囲の量で存在する、実施形態Ｘ又はＹに記載の組成物。
ＡＡ．前記消泡剤が、前記組成物の全重量に基づいて、０．０７５〜０．７５重量％の範囲の量で存在する、実施形態Ｚに記載の組成物。
ＡＢ．前記消泡剤が、前記組成物の全重量に基づいて、０．１５〜０．６重量％の範囲の量で存在する、実施形態ＡＡに記載の組成物。
ＡＣ．顔料を更に含む、実施形態Ａ〜ＡＢ及びＢＥ〜ＢＧのいずれか１つに記載の組成物。
ＡＤ．気密密閉容器であって、弁を介してその内部に封入された実施形態Ａ〜ＡＣ及びＢＥ〜ＢＧのいずれか１つに記載のポリウレタンエアゾール組成物を含む、気密密閉容器と、前記容器から前記ポリウレタンエアゾール組成物を吐出するためのアクチュエータと、を備える、エアゾール装置。
ＡＥ．ポリウレタンエアゾール組成物の製造方法であって、２つのイソシアネート反応性基を含むポリオール又はチオール、及びジイソシアネートを含む混合物を反応させることによって、イソシアネート末端ポリウレタンプレポリマーを得ることと、前記イソシアネート末端プレポリマーを（ｉ）酸性水可溶化化合物と、（ｉｉ）前記水可溶性化合物を中和させるための塩基と、（ｉｉｉ）シリル末端基と、を逐次反応させることによって可溶化ポリウレタンプレポリマーを提供することと、前記可溶化ポリウレタンプレポリマーを水に分散させることと、前記可溶化ポリウレタンプレポリマーを、イソシアネート反応性鎖延長剤と反応させることによって、ポリマーを形成することと、噴射剤を添加して、ポリウレタンエアゾール組成物を得ることと、を含む、ポリウレタンエアゾール組成物の製造方法。
ＡＦ．前記シリル末端基が、以下の式を有するアルコキシシランを含む、実施形態ＡＥに記載の方法：
（Ｒ^２Ｏ）_３ＳｉＲ^３−Ｚ
［式中、Ｒ^２は、水素又はＣ１〜Ｃ４アルキルであり、Ｒ^３は、二価のアルキレン、アルキルアリーレン、又はオキシアルキレンであり、Ｚは、−ＯＨ、−ＳＨ、−ＮＨＲ^４、及び−ＮＨ_２（式中、Ｒ^４は、芳香族又は脂肪族環状基である）から選択される］。
ＡＧ．ポリウレタンエアゾール組成物の製造方法であって、２つのイソシアネート反応性基を含むポリオール又はチオール、及びジイソシアネートを含む混合物を反応させることによって、イソシアネート末端ポリウレタンプレポリマーを得ることと、前記イソシアネート末端ポリウレタンプレポリマーを（ｉ）酸性水可溶化化合物と、（ｉｉ）前記水可溶化化合物を中和させるための塩基と、を逐次反応させることによって、可溶化ポリウレタンプレポリマーを提供することと、前記可溶化ポリウレタンプレポリマーを水に分散させることと、前記可溶化ポリウレタンプレポリマーを、ヒドラジン又はヒドラジドを含むイソシアネート反応性鎖延長剤と反応させることによって、ポリマーを得ることと、噴射剤を添加して、ポリウレタンエアゾール組成物を得ることと、を含む、ポリウレタンエアゾール組成物の製造方法。
ＡＨ．前記ポリマーが、１０，０００ｇ／モル〜２００，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＡＧに記載の組成物。
ＡＩ．前記ポリマーが、１４，０００ｇ／モル〜７５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＡＨに記載の組成物。
ＡＪ．前記塩基が、アルキルアミンを含む、実施形態ＡＥ〜ＡＩのいずれか１つに記載の方法。
ＡＫ．前記イソシアネート反応性鎖延長剤が、ヒドラジン又はヒドラジドを含む、実施形態ＡＥ〜ＡＪのいずれか１つに記載の方法。
ＡＬ．前記ヒドラジドが、カルボヒドラジド、シュウ酸ジヒドラジド、チオカルボヒドラジド、又は以下の式を有するジヒドラジドから選択される、実施形態ＡＫに記載の方法：

(Wherein R is a covalent bond, a heteroatom, or a divalent organic radical).
R. The composition according to any one of embodiments A-Q and BE-BG, further comprising a rheology modifier.
S. The composition according to embodiment R, wherein the rheology modifier is a thickener comprising a urethane block copolymer.
T.A. The composition according to embodiment S, wherein the urethane block copolymer is a hydrophobically modified ethylene oxide-based urethane block copolymer.
U. The composition according to any one of embodiments RT, wherein the rheology modifier is present in an amount ranging from 0.1 to 5% by weight, based on the total weight of the composition.
V. The composition of embodiment U, wherein the rheology modifier is present in an amount ranging from 0.375 to 3% by weight, based on the total weight of the composition.
W. The composition of embodiment V, wherein the rheology modifier is present in an amount ranging from 0.75 to 2.25% by weight, based on the total weight of the composition.
X. The composition according to any one of embodiments A-W and BE-BG, further comprising an antifoam agent.
Y. The composition of Embodiment X, wherein the antifoam agent comprises a modified polyol.
Z. The composition according to embodiment X or Y, wherein the antifoaming agent is present in an amount ranging from 0.01 to 1.2% by weight, based on the total weight of the composition.
AA. The composition of embodiment Z, wherein the antifoaming agent is present in an amount ranging from 0.075 to 0.75% by weight, based on the total weight of the composition.
AB. The composition of Embodiment AA wherein the antifoam is present in an amount ranging from 0.15 to 0.6% by weight, based on the total weight of the composition.
AC. The composition according to any one of embodiments A-AB and BE-BG, further comprising a pigment.
AD. An airtight sealed container comprising the polyurethane aerosol composition according to any one of embodiments A to AC and BE to BG enclosed therein via a valve; An aerosol device comprising: an actuator for discharging a polyurethane aerosol composition.
AE. A process for producing a polyurethane aerosol composition comprising reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing a diisocyanate to obtain an isocyanate-terminated polyurethane prepolymer, Providing a solubilized polyurethane prepolymer by sequentially reacting (i) an acidic water-solubilizing compound, (ii) a base for neutralizing said water-soluble compound, and (iii) a silyl end group. , Forming a polymer by dispersing the solubilized polyurethane prepolymer in water, reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender, and adding a propellant to form a polyurethane. Obtain an aerosol composition DOO DOO, including producing a polyurethane aerosol composition.
AF. The method of embodiment AE, wherein the silyl end group comprises an alkoxysilane having the formula:
_{^{(R 2 O) 3 SiR 3}} -Z
[Wherein R ² is hydrogen or C1-C4 alkyl, R ³ is divalent alkylene, alkylarylene, or oxyalkylene, and Z is —OH, —SH, —NHR ⁴ , and — NH ₂ (wherein R ⁴ is an aromatic or aliphatic cyclic group)].
AG. A method for producing a polyurethane aerosol composition, comprising reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing diisocyanate to obtain an isocyanate-terminated polyurethane prepolymer, and said isocyanate-terminated polyurethane prepolymer Providing a solubilized polyurethane prepolymer by sequentially reacting (i) an acidic water solubilizing compound and (ii) a base for neutralizing the water solubilizing compound; and A polyurethane polymer is obtained by dispersing the prepolymer in water and reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender containing hydrazine or hydrazide, and adding a propellant. Zo It includes obtaining a composition, a method for producing a polyurethane aerosol composition.
AH. The composition of Embodiment AG, wherein the polymer has a weight average molecular weight ranging from 10,000 g / mol to 200,000 g / mol.
AI. The composition of embodiment AH, wherein the polymer has a weight average molecular weight ranging from 14,000 g / mol to 75,000 g / mol.
AJ. The method of any one of embodiments AE to AI, wherein the base comprises an alkylamine.
AK. The method of any one of embodiments AE to AJ, wherein the isocyanate-reactive chain extender comprises hydrazine or hydrazide.
AL. The method of embodiment AK, wherein the hydrazide is selected from carbohydrazide, oxalic dihydrazide, thiocarbohydrazide, or dihydrazide having the formula:

（式中、Ｒは、共有結合、ヘテロ原子、又は二価有機ラジカルである）。
ＡＭ．前記水可溶化化合物が、以下の式によって表される、実施形態ＡＥ〜ＡＬのいずれか１つに記載の方法：
（ＨＢ）_２Ｒ^１ Ａ
［式中、Ｂは、Ｏ、Ｓ、ＮＨ、又はＮＲ（式中、Ｒは、１〜４個の炭素原子を含むアルキル基である）であり、Ｒ^１は、三価有機連結基であり、Ａは、−ＳＯ_３ Ｍ、−ＯＳＯ_３ Ｍ、−ＣＯ_２ Ｍ、及び−ＯＰＯ（ＯＭ）_２（式中、Ｍは、水溶性カチオンである）から選択されるアニオン性基である］。
ＡＮ．前記水溶性カチオンが、Ｈである、実施形態ＡＭに記載の方法。
ＡＯ．前記水が、前記噴射剤を除く前記組成物の全重量に基づいて、５０重量％〜９５重量％の範囲の量で存在する、実施形態ＡＥ〜ＡＮのいずれか１つに記載の方法。
ＡＰ．前記水が、前記噴射剤を除く前記組成物の全重量に基づいて、７０重量％〜９０重量％の範囲の量で存在する、実施形態ＡＯに記載の方法。
ＡＱ．前記水が、前記噴射剤を除く前記組成物の全重量に基づいて、７３重量％〜８５重量％の範囲の量で存在する、実施形態ＡＰに記載の方法。
ＡＲ．前記噴射剤が、ジメチルエーテルを含む、実施形態ＡＥ〜ＡＱのいずれか１つに記載の方法。
ＡＳ．レオロジー調整剤及び前記ポリマーを合わせることを更に含む、実施形態ＡＥ〜ＡＲのいずれか１つに記載の方法。
ＡＴ．前記レオロジー調整剤が、疎水変性エチレンオキシド系ウレタンブロック共重合体を含む増粘剤である、実施形態ＡＳに記載の方法。
ＡＵ．前記ポリウレタン分散液に消泡剤を添加することを更に含み、前記消泡剤が、変性ポリオールを含む、実施形態ＡＥ〜ＡＴのいずれか１つに記載の方法。
ＡＶ．前記可溶化ポリウレタンポリマー及び任意の添加剤が容器に入れられており、弁を有する容器を気密密閉することと、前記噴射剤を前記密閉容器に導入することと、を更に含む、実施形態ＡＥ〜ＡＵのいずれか１つに記載の方法。
ＡＷ．一液型組成物から基材上に架橋ポリウレタンコーティングを提供する方法であって、前記方法は、噴射剤を用いて、エアゾールアクチュエータを通して、前記基材上に水性ポリウレタン分散液を堆積させることであって、前記水性ポリウレタン分散液が、（ｉ）イソシアネート反応性官能基を有するポリオール又はチオールと、（ｉｉ）中和水可溶化化合物と、（ｉｉｉ）ジイソシアネートと、を反応させることによって得られるウレタン部分、シリル末端基、及び水を含む、ことと、前記水を除去して、前記シリル末端基を縮合させることによって、架橋ポリウレタンコーティングを提供することと、を含む、架橋ポリウレタンコーティングを提供する方法。
ＡＸ．前記シリル末端基が、以下の式を有するアルコキシシラン、を含む、実施形態ＡＷに記載の方法：
（Ｒ^２Ｏ）_３ＳｉＲ^３−Ｚ
［式中、Ｒ^２は、水素又はＣ１〜Ｃ４アルキルであり、Ｒ^３は、二価のアルキレン、アルキルアリーレン、又はオキシアルキレンであり、Ｚは、−ＯＨ、−ＳＨ、−ＮＨＲ^４、及び−ＮＨ_２（式中、Ｒ^４は、芳香族又は脂肪族環状基である）から選択される］。
ＡＹ．一液型組成物から基材上に熱可塑性ポリウレタンコーティングを提供する方法であって、前記方法は、噴射剤を用いて、エアゾールアクチュエータを通して、前記基材上に水性ポリウレタン分散液を堆積させることであって、前記水性ポリウレタン分散液が、（ｉ）イソシアネート反応性官能基を有するポリオール又はチオールと、（ｉｉ）中和水可溶化化合物と、（ｉｉｉ）ジイソシアネートと、（ｉｖ）ヒドラジン又はヒドラジド、を含むイソシアネート反応性鎖延長剤と、を反応させることによって得られるポリマーを含む、ことと、前記水を除去して、熱可塑性ポリウレタンコーティングを硬化させることと、を含む、熱可塑性ポリウレタンコーティングを提供する方法。
ＡＺ．前記噴射剤が、ジメチルエーテルを含む、実施形態ＡＷ〜ＡＹのいずれか１つに記載の方法。
ＢＡ．前記ポリウレタンコーティングが、透明である、実施形態ＡＷ〜ＡＺのいずれか１つに記載の方法。
ＢＢ．前記ポリウレタンコーティングが、耐候性試験に供したとき、３２００時間で最高１２％の光沢減少値を示す、実施形態ＡＷ〜ＢＡのいずれか１つに記載の方法。
ＢＣ．前記ポリウレタンコーティングが、耐候性試験に供したとき、３２００時間で最高８％の光沢減少値を示す、実施形態ＢＢに記載の方法。
ＢＤ．前記ポリウレタンコーティングが、耐候性試験に供したとき、３２００時間で最高４％の光沢減少値を示す、実施形態ＢＣに記載の方法。
ＢＥ．ポリマーと水とジメチルエーテル噴射剤と、を含む、ポリウレタンエアゾール組成物であって、前記ポリマーが、（ｉ）イソシアネート反応性官能基を有するポリオール又はチオールと、（ｉｉ）中和水可溶化化合物と、（ｉｉｉ）ジイソシアネートと、（ｉｖ）イソシアネート反応性鎖延長剤と、を反応させることによって得られるポリマーであり、前記ポリマーが、１０，０００ｇ／モル〜２００，０００ｇ／モルの範囲の重量平均分子量を有する、ポリウレタンエアゾール組成物。
ＢＦ．前記ポリマーが、１４，０００ｇ／モル〜１２５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＢＥに記載の組成物。
ＢＧ．前記ポリマーが、２５，０００ｇ／モル〜７５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＢＦに記載の組成物。
ＢＨ．一液型組成物から基材上に熱可塑性ポリウレタンコーティングを提供する方法であって、前記方法は、ジメチルエーテル噴射剤を用いて、エアゾールアクチュエータを通して、前記基材上に水性ポリウレタン分散液を堆積させることであり、前記水性ポリウレタン分散液が、（ｉ）イソシアネート反応性官能基を有するポリオール又はチオールと、（ｉｉ）中和水可溶化化合物と、（ｉｉｉ）ジイソシアネートと、（ｉｖ）イソシアネート反応性鎖延長剤と、を反応させることによって得られるポリマーを含む、ことと、水を除去して、熱可塑性ポリウレタンコーティングを硬化させることであって、を前記ポリマーが、１０，０００ｇ／モル〜２００，０００ｇ／モルの範囲の重量平均分子量を有する、ことと、を含む、熱可塑性ポリウレタンコーティングを提供する方法。
ＢＩ．前記ポリマーが、１４，０００ｇ／モル〜１２５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＢＨに記載の方法。
ＢＪ．前記ポリマーが、２５，０００ｇ／モル〜７５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＢＩに記載の方法。
ＢＫ．ポリウレタンエアゾール組成物の製造方法であって、２つのイソシアネート反応性基を含むポリオール又はチオール、及びジイソシアネートを含む混合物を反応させることによって、イソシアネート末端ポリウレタンプレポリマーを得ることと、前記イソシアネート末端ポリウレタンプレポリマーを（ｉ）酸性水可溶化化合物と、（ｉｉ）前記水可溶化化合物を中和させるための塩基と、を逐次反応させることによって、可溶化ポリウレタンプレポリマーを提供することと、前記可溶化ポリウレタンプレポリマーを水に分散させることと、前記可溶化ポリウレタンプレポリマーをイソシアネート反応性鎖延長剤と反応させることによって、ポリマーを得ることと、ジメチルエーテル噴射剤を添加して、ポリウレタンエアゾール組成物を得ることと、を含み、前記ポリマーが、１０，０００ｇ／モル〜２００，０００ｇ／モルの範囲の重量平均分子量を有する、ポリウレタンエアゾール組成物の製造方法。
ＢＬ．前記ポリマーが、２５，０００ｇ／モル〜７５，０００ｇ／モルの範囲の重量平均分子量を有する、実施形態ＢＫに記載の方法。

(Wherein R is a covalent bond, a heteroatom, or a divalent organic radical).
AM. The method of any one of embodiments AE to AL, wherein the water-solubilizing compound is represented by the following formula:
(HB) ₂ R ¹ A
[Wherein B is O, S, NH, or NR (wherein R is an alkyl group containing 1 to 4 carbon atoms), and R ¹ is a trivalent organic linking group. , A is an anionic group selected from —SO ₃ M, —OSO ₃ M, —CO ₂ M, and —OPO (OM) ₂ , where M is a water-soluble cation].
AN. The method of embodiment AM, wherein the water-soluble cation is H.
AO. The method of any one of embodiments AE to AN, wherein the water is present in an amount ranging from 50% to 95% by weight, based on the total weight of the composition excluding the propellant.
AP. The method of embodiment AO, wherein the water is present in an amount ranging from 70% to 90% by weight, based on the total weight of the composition excluding the propellant.
AQ. The method of embodiment AP, wherein the water is present in an amount ranging from 73% to 85% by weight, based on the total weight of the composition excluding the propellant.
AR. The method of any one of embodiments AE-AQ, wherein the propellant comprises dimethyl ether.
AS. The method of any one of embodiments AE-AR, further comprising combining a rheology modifier and the polymer.
AT. The method of embodiment AS, wherein the rheology modifier is a thickener comprising a hydrophobically modified ethylene oxide-based urethane block copolymer.
AU. The method of any one of embodiments AE-AT, further comprising adding an antifoam to the polyurethane dispersion, wherein the antifoam comprises a modified polyol.
AV. Embodiments AE- wherein the solubilized polyurethane polymer and optional additives are contained in a container, further comprising hermetically sealing a container having a valve and introducing the propellant into the sealed container. The method according to any one of the AUs.
AW. A method of providing a crosslinked polyurethane coating on a substrate from a one-part composition, the method comprising depositing an aqueous polyurethane dispersion on the substrate through an aerosol actuator using a propellant. The aqueous polyurethane dispersion is a urethane part obtained by reacting (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water-solubilizing compound, and (iii) diisocyanate. A method for providing a crosslinked polyurethane coating comprising: silyl end groups, and water; and providing the crosslinked polyurethane coating by removing the water and condensing the silyl end groups.
AX. The method of embodiment AW, wherein the silyl end group comprises an alkoxysilane having the formula:
^{_{(R 2 O) 3 SiR 3}} -Z
[Wherein R ² is hydrogen or C1-C4 alkyl, R ³ is divalent alkylene, alkylarylene, or oxyalkylene, and Z is —OH, —SH, —NHR ⁴ , and — NH ₂ (wherein R ⁴ is an aromatic or aliphatic cyclic group)].
AY. A method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition, the method comprising depositing an aqueous polyurethane dispersion on the substrate through an aerosol actuator using a propellant. Wherein the aqueous polyurethane dispersion comprises (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water solubilizing compound, (iii) diisocyanate, and (iv) hydrazine or hydrazide. Providing a thermoplastic polyurethane coating comprising: a polymer obtained by reacting an isocyanate-reactive chain extender comprising: and removing the water to cure the thermoplastic polyurethane coating. Method.
AZ. The method of any one of embodiments AW to AY, wherein the propellant comprises dimethyl ether.
BA. The method of any one of embodiments AW to AZ, wherein the polyurethane coating is transparent.
BB. The method of any one of embodiments AW-BA, wherein the polyurethane coating exhibits a gloss reduction value of up to 12% in 3200 hours when subjected to a weather resistance test.
BC. The method of embodiment BB, wherein the polyurethane coating exhibits a gloss reduction value of up to 8% at 3200 hours when subjected to a weather resistance test.
BD. The method of embodiment BC, wherein the polyurethane coating exhibits a gloss reduction value of up to 4% in 3200 hours when subjected to a weathering test.
BE. A polyurethane aerosol composition comprising a polymer, water and a dimethyl ether propellant, wherein the polymer is (i) a polyol or thiol having an isocyanate-reactive functional group, and (ii) a neutralized water-solubilizing compound. (Iii) a polymer obtained by reacting diisocyanate with (iv) an isocyanate-reactive chain extender, wherein the polymer has a weight average molecular weight in the range of 10,000 g / mol to 200,000 g / mol. A polyurethane aerosol composition comprising:
BF. The composition of embodiment BE, wherein the polymer has a weight average molecular weight ranging from 14,000 g / mol to 125,000 g / mol.
BG. The composition of embodiment BF, wherein the polymer has a weight average molecular weight ranging from 25,000 g / mole to 75,000 g / mole.
BH. A method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition, the method comprising depositing an aqueous polyurethane dispersion on the substrate through an aerosol actuator using a dimethyl ether propellant. And the aqueous polyurethane dispersion comprises (i) a polyol or thiol having an isocyanate-reactive functional group, (ii) a neutralized water-solubilizing compound, (iii) a diisocyanate, and (iv) an isocyanate-reactive chain extension. A polymer obtained by reacting with an agent, and removing water to cure the thermoplastic polyurethane coating, wherein the polymer is from 10,000 g / mol to 200,000 g / A thermoplastic polyurethane having a weight average molecular weight in the range of moles A method for providing a down coating.
BI. The method of embodiment BH, wherein the polymer has a weight average molecular weight ranging from 14,000 g / mol to 125,000 g / mol.
BJ. The method of embodiment BI, wherein the polymer has a weight average molecular weight in the range of 25,000 g / mol to 75,000 g / mol.
BK. A method for producing a polyurethane aerosol composition, comprising reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing diisocyanate to obtain an isocyanate-terminated polyurethane prepolymer, and said isocyanate-terminated polyurethane prepolymer Providing a solubilized polyurethane prepolymer by sequentially reacting (i) an acidic water solubilizing compound and (ii) a base for neutralizing the water solubilizing compound; and A polyurethane aerosol composition can be obtained by dispersing the prepolymer in water, reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender, and adding a dimethyl ether propellant. When, wherein the said polymer has a weight average molecular weight in the range of 10,000 g / mol ～200,000G / mol, the production method of the polyurethane aerosol composition.
BL. The method of embodiment BK, wherein the polymer has a weight average molecular weight in the range of 25,000 g / mol to 75,000 g / mol.

  Unless otherwise noted, all parts, percentages (%), ratios, etc. in the examples and the rest of the specification are by weight and all reagents used in the examples are from general chemical suppliers. For example, obtained or available from Sigma-Aldrich Company (Saint Louis, Missouri), or may be synthesized by conventional methods.

  Examples will be described using the following abbreviations.

  AMEO: 3-aminopropyltriethoxysilane obtained from Evonik Industries AG (Essen, Germany) under the trade name “DYNASYLAN AMEO”.

  CDH: 1,3-diaminourea obtained from Sigma-Aldrich Company as another name “CARBOHYDRAZIDE, 98%”.

  CHDM: cyclohexa-1,4-ylene diamine obtained from Eastman Chemical Company (Kingsport, Tennessee).

  DBTDA: Dibutyltin diacetate obtained from Sigma-Aldrich Company.

  DF-1760: Elementis Specialties, Inc. An antifoaming agent obtained from (Hightown, New Jersey) under the trade name “DAPRO DF-1760”.

  DMDW: Bis (4-isocyanatocyclohexyl) methane obtained from Bayer Material Science AG (Leverkusen, Germany) under the trade name “DESMODUR W”.

  DME: dimethyl ether obtained from Aeropres Corporation (Shreveport, Louisiana).

  DMPA: [(2,6-dimethylphenyl) amino] (oxo) acetic acid obtained from Tokyo Chemical Industry (Tokyo, Japan).

  EDA: ethylenediamine obtained from Alfa-Aesar (Ward Hill, Massachusetts).

  I-1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] obtained from BASF SE (Ludwigshafen am Rhein, Germany) under the trade name “IRGANOX 1010”.

  KCG: A biocide obtained from Dow Chemical Company (Midland, Michigan) under the trade name “KATHON CG / ICP”.

  MEK: methyl ethyl ketone.

  PBZ: Lonza Group Ltd. (Basel, Switzerland) Biocide obtained under the trade name “PROXEL BZ PLUS”.

  PPG-2000: polyether polyol obtained from Bayer Material Science AG under the trade name “ARCOL PPG-2000”.

  RM-12W: a nonionic rheology modifier obtained from Dow Chemical Company under the trade name “ACRYSOL RM-12W”.

  RU-13-825: Stahl Holdings, b. v. (Walwijk, Netherlands), a polyurethane dispersion obtained under the trade name “RU 13-825”.

  T-292: A hindered amine light stabilizer obtained from BASF (Charlotte, North Carolina) under the trade name “TINUVIN 292”.

  T-405: UV absorber obtained from BASF (Charlotte, North Carolina) under the trade name “TINUVIN 405”.

  TEA: triethylamine.

  TG-403: Transparent surface control additive obtained from Evonik Industries under the trade name “TEGO GLIDE 403”.

  V-220: Polyether polyol obtained from Dow Chemical Company under the trade name “VORANOL 220-056N”.

  XR-5508: Stahl Holdings, b. v. A carbodiimide cross-linking agent obtained under the trade name “XR 5508”.

Polyurethane dispersion PD-1
An aqueous polyurethane dispersion was prepared as follows. 101.74 g (g) V-220 and 51.84 g DMDW were added to a 500 mL 3-neck round bottom flask equipped with a mechanical stirrer, condenser and argon inlet. About 0.04 g DBTDA was added to the flask and the mixture was heated to 78 ° C. under argon with stirring and held for 1 hour. 6.40 g DMPA and 41.70 g MEK were added and the mixture was held at 85 ° C. for about 3 hours until the DMPA dissolved. 7.67 g of CHDM was added to the flask and stirring continued for another 2 hours before the solution was cooled to about 25 ° C. and then diluted with 91.5 g of acetone. While maintaining stirring, 4.84 g TEA, 1.67 g I-1010, 1.67 g T-292, and 3.34 g T-405 were added and the solution was held for 30 minutes to allow isocyanate end A prepolymer was obtained. 340 g of distilled water was added to a 1000 mL 3-neck round bottom flask equipped with a mechanical stirrer, thermometer, and argon inlet. While stirring the water at 650 rpm, the prepolymer solution was transferred to the flask using a dropping funnel at 21 ° C. for about 30 minutes. The stirrer speed was increased to 400 rpm and 2.44 g CDH was added. After a pre-mix of 0.55 g EDA in 1.28 g distilled water was added dropwise to the flask over about 5 minutes, the dispersion was heated to 50 ° C. and held for 1 hour. 0.16 g DF-1760 was added and then MEK and acetone were removed using a rotary evaporator at 40 ° C. and 5.33 kPa vacuum. The resulting aqueous dispersion was about 35% by weight polyurethane.

PD-2
An aqueous silane-terminated polyurethane dispersion was prepared as follows. 368.10 g of PPG-2000 and 188.61 g of DMDW were added to a 2 liter 3-neck round bottom flask equipped with a mechanical stirrer, condenser and argon inlet. About 0.15 g of DBTDA was added to the flask and the mixture was heated to 78 ° C. under argon with stirring and held for 30 minutes. 23.18 g DMPA and 151.35 g MEK were added and the mixture was held at 85 ° C. for about 2.5 hours until the DMPA dissolved. 25.77 g CHDM was added to the flask and stirring continued for an additional 1.5 hours before the solution was cooled to about 25 ° C. and then diluted with 339 g acetone. While maintaining stirring, 17.52 g TEA, 3.02 g I-1010, and 6.05 g T-292 were added and the solution was held for 30 minutes. 6.09 g AMEO was added and stirring was continued for another 30 minutes to obtain an isocyanate-terminated prepolymer. 1,200 g of distilled water was added to a 3 liter 3-neck round bottom flask equipped with a mechanical stirrer, thermometer and argon inlet. While stirring water at 300 rpm, the prepolymer solution was transferred to the flask using a dropping funnel at 21 ° C. for about 30 minutes. After a premix of 8.94 g CDH in 50.1 g of distilled water is added dropwise to the flask over about 5 minutes, a second premix of 2.01 g EDA in 11.25 g of distilled water is also added to the flask over about 5 minutes. It was dripped in. The dispersion was then heated to 50 ° C. and held for 1 hour. 0.60 g DF-1760 was added and then MEK and acetone were removed using a rotary evaporator at 40 ° C. and 5.33 kPa vacuum. The resulting aqueous dispersion was about 35% by weight silane terminated polyurethane.

PD-3
An aqueous silane-terminated polyether polyurethane dispersion was prepared as follows. 63.62 g V-220 and 32.35 g DMDW were added to a 500 mL 4-neck round bottom flask equipped with a mechanical stirrer, thermometer, condenser, and nitrogen inlet. About 0.02 g of DBTDA was added to the flask and the mixture was heated to 78 ° C. under nitrogen with stirring and held for 1 hour. 4.0 g DMPA and 20.0 g MEK were added and the mixture was held at 85 ° C. for about 3 hours until the DMPA dissolved. The isocyanate content of the prepolymer was determined by standard dibutylamine back titration method. In obtaining the theoretical isocyanate value, 4.78 g of CHDM was added to the flask and stirring continued for another 2 hours before the solution was cooled to about 40 ° C. and then diluted with 60 g of acetone. While maintaining stirring, 3.02 g TEA was added and the solution was held for 30 minutes. 5.53 g AMEO was then added and stirring continued for an additional 20 minutes, followed by the addition of a premix of 1.53 g CDH in 8.0 g distilled water. After 10 minutes, 190 g of distilled water at about 5-10 ° C. was slowly added with vigorous stirring to obtain an aqueous dispersion. A premix of 0.34 g EDA in 5.0 g distilled water was slowly added and stirring was continued at 21 ° C. for 1 hour. Then, MEK and acetone were removed using a rotary evaporator at 40 ° C. and a vacuum of 5.33 kPa. The resulting aqueous silane-terminated polyether-based polyurethane dispersion was about 35% by weight polyether-based polyurethane.

PD-4
An aqueous silane-terminated polyether polyurethane dispersion was prepared as follows. 60.51 g V-220 and 35.48 g DMDW were added to a 500 mL 4-neck round bottom flask equipped with a mechanical stirrer, thermometer, condenser and nitrogen inlet. About 0.02 g of DBTDA was added to the flask and the mixture was heated to 78 ° C. under nitrogen with stirring and held for 1 hour. 4.0 g DMPA and 20.0 g MEK were added and the mixture was held at 85 ° C. for about 3 hours until the DMPA dissolved. The isocyanate content of the prepolymer was determined by standard dibutylamine back titration method. In obtaining the theoretical NCO value, 5.23 g of CHDM was added to the flask and stirring continued for another 2 hours before the solution was cooled to about 40 ° C. and then diluted with 60 g of acetone. While maintaining stirring, 3.02 g TEA was added and the solution was held for 30 minutes, then partially terminated with 3.35 g AMEO and stirring was continued for another 20 minutes. 1.0 g I-1010 and 2.0 g T-292 were added, followed by a pre-mix of 0.78 g CDH in 10.0 g distilled water. After 5 minutes, 200 g of distilled water at about 5-10 ° C. was slowly added with vigorous stirring to obtain an aqueous dispersion. A pre-mix of 0.79 g EDA in 6.0 g distilled water was added slowly and stirring was continued at 21 ° C. for 1 hour. Then, MEK and acetone were removed using a rotary evaporator at 40 ° C. and a vacuum of 5.33 kPa. The resulting aqueous silane-terminated polyether-based polyurethane dispersion was about 35% by weight polyether-based polyurethane.

PD-5
Aqueous polyether-based polyurethane dispersions were prepared generally according to the method described in PD-3, excluding AMEO from the synthesis.

Example 1
165.63 g deionized water, 1.58 g DF-1760, 14.01 g RM-12W, and 218.0 g PD-1 were added sequentially to a 500 mL plastic beaker, and IKA Works, Inc. Dispersion was carried out at 21 ° C. for 5 minutes with moderate shear using a vortex mixer model “MV1 MINI VORTEXER” obtained from (Wilmington, North Carolina). 240 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Next, using a model “3SB” bullet pressure filter obtained from Aero-Tech Laboratory Equipment Company, LLC (Lebanon, Missouri), and a male actuator attached to the female valve, 80 g of DME was added to the aerosol can. Added.

(Example 2)
864.3 g deionized water, 2.02 g DF-1760, 40.05 g RM-12W, and 1,04.1 g PD-2 in one gallon (3.785 liter) plastic beaker in sequence. Added and dispersed with moderate shear at 21 ° C. for 5 minutes using a vortex mixer. 383 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 128 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

(Example 3)
86.43 g deionized water, 0.22 g DF-1760, 4.03 g RM-12W, and 109.46 g PD-3 were added sequentially to a 500 mL plastic beaker and 21 using a vortex mixer. Dispersed with moderate shear at 5 ° C. for 5 minutes. 120 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 40 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

Example 4
57.66 g deionized water, 0.55 g DF-1760, 5.00 g RM-12W, and 76.74 g PD-4 were added sequentially to a 250 mL plastic beaker and 21 using a vortex mixer. Dispersed with moderate shear at 5 ° C. for 5 minutes. 120 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 40 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

Comparative Example A
286.97 g of deionized water, 3.61 g of DF-1760, 0.62 g of KCG, and 21.33 g of RM-12W, and 287.60 g of RU-13-825, one after another in a 1 liter plastic beaker. And dispersed with moderate shear at 21 ° C. for 5 minutes using a vortex mixer. 383 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 128 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

Comparative Example B
86.43 g deionized water, 0.22 g DF-1760, 4.03 g RM-12W, and 109.44 g PD-5 were added sequentially to a 500 mL plastic beaker and 21 using a vortex mixer. Dispersed with moderate shear at 5 ° C. for 5 minutes. 120 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 40 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

Comparative Example C
46.38 g deionized water, 1.84 g DF-1760, 10.70 g RM-12W, 211.16 g RU-13-825, and 30.06 g XR-5508 in turn to a 500 mL plastic beaker. And dispersed with moderate shear at 21 ° C. for 5 minutes using a vortex mixer. 120 g of this mixture was transferred to an aerosol can followed by a glass mixing marble, the female valve was closed and the can was crimped. Then 40 g of DME was added to the aerosol can using a burette pressure filter and a male actuator attached to the female valve.

Test Method Test Panel Preparation Test panels were prepared by spraying the aerosol composition onto both black and white automotive painted panels and drying at 21 ° C. for 24 hours. The dried film thickness was about 2 mils (about 50.8 μm).

Glossiness The glossiness of the test panel was measured at 60 degrees using a model “4601 HAZE-GLOSS REFECTOMETER” obtained from Byk-Gardener GmbH (Geretsried, Germany).

Weight average molecular weight Measured by size exclusion chromatography (SEC) using a model "e2695" pump / autosampler from Waters Corporation (Milford, Massachusetts) equipped with a PL-Gel-2 column, against standard polystyrene of narrow molecular weight And calibrated.

Weatherability Test The prepared test panels were weathered according to ISO 4882-2 (2013), the entire contents of which are incorporated herein. ISO 4892-2 (2013), Method A, Cycle No. 4 is 0.55W. The shift of narrow band irradiance (340 nm) was followed with a spectral irradiance of m ⁻² nm ⁻¹ . In addition, the following changes were recorded during the drying cycle portion of the test. The black panel temperature was 70 ° C. and the chamber temperature was 47 ° C. The gloss and color change of the weathered test panel was measured at various time intervals.

Water Resistance—Visual Method The prepared test panel was immersed in 2 inches (5 centimeters) of distilled water. The time taken for the color or opacity of the coating to change visually was recorded. This is known as the water resistant time.

Water Resistance—Colorimeter Method The color of the prepared test panel was measured before and after immersion in distilled water at 21 ° C. for 18 hours using a 45 ° angle MA6811 spectrophotometer equipped with a D65 / 10 light source. Subsequently, the color change (ΔE) before and after immersion was determined (water resistance ΔE).

  The results are shown in the table below.

  All of the above patents and patent applications are expressly incorporated herein by reference. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the following claims and their equivalents.

Claims (18)

A polyurethane aerosol composition comprising a polymer, water and a propellant, comprising:
The polymer is
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
(Iv) an isocyanate-reactive chain extender comprising hydrazine or hydrazide;
A polyurethane aerosol composition, which is a polymer obtained by reacting. A polyurethane aerosol composition comprising a urethane moiety, a silyl end group, water and a propellant,
The urethane portion is
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
A polyurethane aerosol composition, which is a urethane part obtained by reacting with The composition of claim 2, wherein the silyl end group comprises an alkoxysilane having the formula:
_{^{(R 2 O) 3 SiR 3}} -Z
Wherein R ² is hydrogen or C ₁ -C ₄ alkyl, R ³ is divalent alkylene, alkylarylene, oxyalkylene, Z is —OH, —SH, —NHR ⁴ , and —NH ₂ (wherein R ⁴ is an aromatic or aliphatic cyclic group)]. The composition according to any one of claims 1 to 3, wherein the neutralized water solubilizing compound comprises a reaction product of the following formula:
(HB) ₂ R ¹ A
Wherein B is O, S, NH or NR (wherein R is an alkyl group containing 1 to 4 carbon atoms), R ¹ is a trivalent organic linking group; a _{is, -SO 3 M, -OSO 3 M} , -CO 2 M, and -OPO _{(OM) 2} (wherein, M is a is a water-soluble cation) is an anionic group selected from.   5. A composition according to any one of the preceding claims, wherein the water is present in an amount ranging from 50% to 95% by weight, based on the total weight of the composition excluding the propellant.   The composition according to any one of claims 1 to 5, wherein the propellant comprises dimethyl ether.   The composition of claim 2 further comprising a urea moiety obtained by reacting an isocyanate-terminated prepolymer with an isocyanate-reactive chain extender.   The composition according to claim 7, wherein the isocyanate-reactive chain extender is hydrazine or hydrazide. 9. The composition of claim 8, wherein the hydrazide is selected from carbodihydrazide, oxalic acid dihydrazide, thiocarbohydrazide, or dihydrazide having the formula:

(Wherein R is a covalent bond, a heteroatom, or a divalent organic radical). An airtight hermetically sealed container comprising the polyurethane aerosol composition according to any one of claims 1 to 9 enclosed therein via a valve;
An actuator for discharging the polyurethane aerosol composition from the container;
An aerosol device comprising: A method for producing a polyurethane aerosol composition comprising:
Obtaining an isocyanate-terminated polyurethane prepolymer by reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing diisocyanate;
The isocyanate-terminated polyurethane prepolymer (i) an acidic water solubilizing compound;
(Ii) a base for neutralizing the water solubilizing compound;
Providing a solubilized polyurethane prepolymer by sequentially reacting
Dispersing the solubilized polyurethane prepolymer in water;
Reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender comprising hydrazine or hydrazide;
Adding a propellant to obtain a polyurethane aerosol composition;
A process for producing a polyurethane aerosol composition, comprising: A method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition comprising:
Depositing an aqueous polyurethane dispersion on the substrate using a propellant through an aerosol actuator, the aqueous polyurethane dispersion comprising:
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
(Iv) comprising a polymer obtained by reacting an isocyanate-reactive chain extender comprising hydrazine or hydrazide;
Removing water from the dispersion to cure the thermoplastic polyurethane coating;
A method for providing a thermoplastic polyurethane coating comprising: A method for producing a polyurethane aerosol composition comprising:
Obtaining an isocyanate-terminated polyurethane prepolymer by reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing diisocyanate;
The isocyanate-terminated polyurethane prepolymer (i) an acidic water solubilizing compound;
(Ii) a base for neutralizing the water-soluble compound;
(Iii) a silyl end group;
Providing a solubilized polyurethane prepolymer by sequentially reacting
Dispersing the solubilized polyurethane prepolymer in water;
Reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender;
Adding a propellant to obtain a polyurethane aerosol composition;
A process for producing a polyurethane aerosol composition, comprising: A method for providing a crosslinked polyurethane coating on a substrate from a one-part composition comprising:
Depositing an aqueous polyurethane dispersion on the substrate with a propellant through an aerosol actuator,
The aqueous polyurethane dispersion is
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
Urethane part obtained by reacting,
Including silyl end groups, and water,
Providing a crosslinked polyurethane coating by removing the water and condensing the silyl end groups;
A method of providing a crosslinked polyurethane coating comprising: 15. A method according to claim 13 or 14, wherein the silyl end group comprises an alkoxysilane having the formula:
_{^{(R 2 O) 3 SiR 3}} -Z
[Wherein R ² is hydrogen or C1-C4 alkyl, R ³ is divalent alkylene, alkylarylene, or oxyalkylene, and Z is —OH, —SH, —NHR ⁴ , and — NH ₂ (wherein R ⁴ is an aromatic or aliphatic cyclic group)]]. A polyurethane aerosol composition comprising a polymer, water and a dimethyl ether propellant,
The polymer is
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
(Iv) an isocyanate-reactive chain extender;
A polymer obtained by reacting
A polyurethane aerosol composition wherein the polymer has a weight average molecular weight in the range of 10,000 g / mole to 200,000 g / mole. A method of providing a thermoplastic polyurethane coating on a substrate from a one-part composition comprising:
Depositing an aqueous polyurethane dispersion on the substrate using a dimethyl ether propellant through an aerosol actuator, the aqueous polyurethane dispersion comprising:
(I) a polyol or thiol having an isocyanate-reactive functional group;
(Ii) a neutralized water solubilizing compound;
(Iii) diisocyanate;
(Iv) an isocyanate-reactive chain extender;
Including a polymer obtained by reacting with
Removing water from the dispersion to cure the thermoplastic polyurethane coating,
The polymer has a weight average molecular weight in the range of 10,000 g / mol to 200,000 g / mol;
A method for providing a thermoplastic polyurethane coating comprising: A method for producing a polyurethane aerosol composition comprising:
Obtaining an isocyanate-terminated polyurethane prepolymer by reacting a polyol or thiol containing two isocyanate-reactive groups and a mixture containing diisocyanate;
The isocyanate-terminated polyurethane prepolymer (i) an acidic water solubilizing compound;
(Ii) a base for neutralizing the water solubilizing compound;
Providing a solubilized polyurethane prepolymer by sequentially reacting
Dispersing the solubilized polyurethane prepolymer in water;
Reacting the solubilized polyurethane prepolymer with an isocyanate-reactive chain extender;
Adding a propellant to obtain a polyurethane aerosol composition;
The polymer has a weight average molecular weight in the range of 10,000 g / mole to 200,000 g / mole,
A method for producing a polyurethane aerosol composition.